KR102059754B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention is a polycarbonate resin; Rubber modified vinyl graft copolymers; Large particle rubbery polymers having an average particle size of 400 to 1,500 nm; Aromatic vinyl copolymer resins; Phosphorus flame retardants; Talc; Wollastonite; Rubbery polymers in which maleic anhydride is graft polymerized; And a black pigment. The thermoplastic resin composition is excellent in adhesion to metals, rigidity, flame retardancy, fluidity, appearance characteristics, and the like.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND ARTICLE PRODUCED THEREFROM}

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent adhesion to metals, rigidity, flame retardancy, fluidity, appearance characteristics, and the like and molded articles prepared therefrom.

The thermoplastic resin composition has a specific gravity lower than that of glass and metal, and is excellent in physical properties such as formability and impact resistance, and thus is useful in housings, interior / exterior materials for automobiles, exterior materials for buildings, and the like. In particular, with the recent trend toward larger and lighter electrical and electronic products, plastic products using thermoplastic resins are rapidly replacing the existing glass and metal areas.

Among these thermoplastic resin compositions, a PC / ABS thermoplastic resin composition obtained by mixing a rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene (ABS) copolymer resin with a polycarbonate (PC) resin is a polycarbonate resin. It is possible to improve workability, chemical resistance, etc. without reducing impact resistance, heat resistance, and the like, and to reduce costs.

In addition, since the thermoplastic resin composition has excellent adhesion to metals, the thermoplastic resin composition may be applied to various applications including exterior materials of portable devices, and thus, research to improve adhesion to metals is required, and improvements in rigidity, flame retardancy, and the like are required. For the purpose, inorganic fillers such as glass fibers, talc, wollastonite, flame retardants and the like can be included.

However, thermoplastic resin compositions to which inorganic fillers, such as glass fibers, are applied may have low fluidity, elongation, and the like, and glass fibers, etc. may protrude, making it difficult to implement high appearance characteristics.

Accordingly, there is a need for development of a thermoplastic resin composition having excellent adhesion to metals, rigidity, flame retardancy, fluidity, appearance characteristics, and the like.

Background art of the present invention is disclosed in Japanese Patent Laid-Open No. 2015-028135 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in adhesion to metals, rigidity, flame retardancy, flowability, appearance characteristics and the like.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is a polycarbonate resin; Rubber modified vinyl graft copolymers; Large particle rubbery polymers having an average particle size of 400 to 1,500 nm; Aromatic vinyl copolymer resins; Phosphorus flame retardants; Talc; Wollastonite; Rubbery polymers in which maleic anhydride is graft polymerized; And black pigments.

2. In one embodiment, the thermoplastic resin composition is 100 parts by weight of the polycarbonate resin; 1 to 10 parts by weight of the rubber-modified vinyl graft copolymer; 0.5 to 5 parts by weight of the large particle rubbery polymer; 3 to 20 parts by weight of the aromatic vinyl copolymer resin; 10 to 30 parts by weight of the phosphorus flame retardant; 3 to 25 parts by weight of the talc; 5 to 20 parts by weight of the wollastonite; 0.01 to 5 parts by weight of the rubbery polymer graft polymerized maleic anhydride; And it may include 0.05 to 3 parts by weight of the black pigment.

3. In the above 1 or 2 embodiment, the rubber modified vinyl graft copolymer is a graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer having an average particle size of 100 to 600 nm. It may have been.

4. In the above 1-3 embodiments, the large-diameter rubbery polymer and the aromatic vinyl copolymer resin copolymerize with the rubbery polymer, aromatic vinyl monomer and the aromatic vinyl monomer having a viscosity of 150 cps or more in a 5% by weight styrene solution. Thermoplastic resin composition in the form of a rubber-modified aromatic vinyl copolymer resin (a mixture of a large particle size rubbery polymer having a mean particle size of 400 to 1,500 nm and a continuous aromatic vinyl copolymer resin) prepared by continuous solution polymerization of possible monomers. Can be included.

5. In the above 1 to 4 embodiments, the aromatic vinyl copolymer resin may be a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

6. In the above 1 to 5 embodiments, the phosphorus flame retardant may include one or more of phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds and phosphazene compounds.

7. In the above 1 to 6 embodiments, the weight ratio of the talc and wollastonite may be 1: 0.3 to 1: 2.

8. In the above 1 to 7, wherein the maleic anhydride graft polymerized rubbery polymer is ethylene-octene rubber (MAH-g-EOR), the maleic anhydride graft polymerized Ethylene-butene rubber (MAH-g-EBR), ethylene-propylene-diene monomer terpolymer (MAH-g-EPDM) graft polymerized maleic anhydride, styrene-ethylene-butadiene graft polymerized maleic anhydride At least one of -styrene copolymer (MAH-g-SEBS), polypropylene (maleic anhydride) graft-polymerized (MAH-g-PP) and polyethylene (maleic anhydride) graft-polymerized (MAH-g-PE) It may include.

9. In the above 1 to 8 embodiments, the average particle size of the black pigment may be 10 to 24 nm.

10. In the above embodiments 1 to 9, the thermoplastic resin composition is bonded to the 100 mm × 25 mm × 2 mm injection molded specimens with an adhesive such that the 25 mm × 25 mm area overlaps the same size metal specimens in accordance with ASTM D1002 Then, the adhesive site is heated at 80 ° C. for 120 seconds, and then aged at room temperature for 5 minutes, and then the measured adhesive strength (shear strength) may be 140 to 300 kgf / cm ² .

11 In the embodiments 1 to 10, the thermoplastic resin composition may have a flame retardancy of 1.0 mm thick specimen measured by the UL-94 vertical test method of V-1 or more.

12. In the above 1 to 11 embodiments, the thermoplastic resin composition has a melt flow index (MI) of 30 to 60 g / 10 minutes measured at 220 ℃ and 5 kgf conditions in accordance with ASTM D1238 have.

13. Another aspect of the present invention relates to a molded article. The molded article is formed from the thermoplastic resin composition according to any one of the above 1 to 12.

14. In the thirteenth embodiment, the molded article may be a plastic member of an electronics housing including a metal frame and a plastic member in contact with at least one surface of the metal frame.

This invention has the effect of providing the thermoplastic resin composition excellent in adhesive force with metal, rigidity, flame retardancy, fluidity | liquidity, appearance characteristics, etc., and the molded article formed therefrom.

1 is a schematic cross-sectional view of an electronics housing according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention includes (A) a polycarbonate resin; (B) rubber modified vinyl graft copolymers; (C) large particle rubbery polymers; (D) aromatic vinyl copolymer resin; (E) phosphorus-based flame retardants; (F) talc; (G) wollastonite; (H) a rubbery polymer in which maleic anhydride is graft polymerized; And (I) a black pigment.

In the present specification, "a to b" indicating a numerical range is defined as "≥a and <b".

(A) polycarbonate resin

As the polycarbonate resin according to one embodiment of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with precursors such as phosgene, halogen formate, and carbonic acid diester can be used.

In an embodiment, the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane and the like can be exemplified, but is not limited thereto. For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, or 1,1-bis (4-hydroxyphenyl ) Cyclohexane can be used, and specifically, 2, 2-bis (4-hydroxyphenyl) propane called bisphenol-A can be used.

In embodiments, the polycarbonate resin may be a branched chain, for example, 0.05 to 2 mol% of a trivalent or more polyfunctional compound, specifically, 3 to the total diphenols used for polymerization It is also possible to use a branched polycarbonate resin prepared by adding a compound having a phenol group or more.

In an embodiment, the polycarbonate resin may be used in the form of a homo polycarbonate resin, a copolycarbonate resin or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid.

In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 10,000 to 50,000 g / mol, for example, 15,000 to 40,000 g / mol. In the above range, the flowability (processability) of the thermoplastic resin composition may be excellent.

In an embodiment, the polycarbonate resin may have a melt flow index (MI) of 10 to 110 g / 10 min, measured at 300 ° C. and 1.2 kg load conditions, based on ISO 1133. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices.

(B) Rubber-modified vinyl graft copolymer

Rubber modified vinyl graft copolymer according to an embodiment of the present invention is to improve the impact resistance, chemical resistance, etc. of the thermoplastic resin composition, a monomer comprising an aromatic vinyl monomer and a vinyl cyanide monomer in the rubber polymer The mixture may be graft polymerized. For example, the rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer in the rubbery polymer, and, if necessary, processability to the monomer mixture. And a monomer imparting heat resistance, thereby graft polymerization. The polymerization may be carried out by known polymerization methods such as emulsion polymerization and suspension polymerization. In addition, the rubber-modified vinyl graft copolymer may form a core (rubber polymer) -shell (copolymer of monomer mixture) structure.

In an embodiment, the rubbery polymer is a diene rubber (rubber polymer) such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), a saturated rubber hydrogenated to the diene rubber, isoprene rubber , Acrylic rubber such as polybutyl acrylate (rubber polymer), ethylene-propylene-diene monomer terpolymer (EPDM) and the like can be exemplified, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. For example, a diene rubber, an acrylic rubber, etc. can be used, Specifically, a polybutadiene, polybutyl acrylate, etc. can be used.

In embodiments, the rubbery polymer (rubber particles) may have an average particle size (z-average) measured by particle size analyzer of 100 to 600 nm, for example 300 to 500 nm. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulum generated during the polymerization of the rubber polymer, and 0.5 g of latex and 30 ml of distilled water are poured into a 1,000 ml flask and filled with distilled water to prepare a sample. 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured by a light scattering particle size analyzer (nano-zs, Malvern).

In embodiments, the content of the rubbery polymer may be 20 to 70% by weight, for example 30 to 65% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, the monomer mixture (aromatic vinyl monomer and The content of the vinyl cyanide monomer) may be 30 to 80% by weight, for example 35 to 70% by weight, based on 100% by weight of the total rubber-modified vinyl graft copolymer. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.

In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be illustrated. These may be used alone or in combination of two or more thereof. The content of the aromatic vinyl monomer may be 10 to 90% by weight, for example 40 to 90% by weight, of 100% by weight of the monomer mixture. In the above range, the processability, impact resistance, and the like of the thermoplastic resin composition may be excellent.

In one embodiment, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. It can be illustrated. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be 10 to 90% by weight, for example 10 to 60% by weight, of 100% by weight of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.

In a specific example, monomers for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like. When using the monomer for imparting the processability and heat resistance, the content may be 15% by weight or less, for example 0.1 to 10% by weight of 100% by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without deteriorating other physical properties.

In an embodiment, the rubber-modified vinyl graft copolymer may include acrylonitrile-butadiene-styrene graft copolymer (g-ABS), acrylate-styrene-acrylonitrile graft copolymer (g-ASA), and the like. It can be illustrated.

In an embodiment, the rubber-modified vinyl graft copolymer may be included in an amount of 1 to 10 parts by weight, for example, 3 to 7 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may have excellent appearance characteristics, impact resistance, fluidity (molding processability), and the like.

(C) Large particle rubbery polymer and (D) aromatic vinyl copolymer resin

The large particle size rubbery polymer according to one embodiment of the present invention has an average particle size (z-average) of 400 to 1,500 nm, for example, 500 to 1,000 nm, specifically 500 to 650 nm, as measured by a particle size analyzer. It is possible to improve the adhesive strength, rigidity, appearance characteristics and the like of the resin composition with the metal. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulum generated during the polymerization of the rubber polymer, and 0.5 g of latex and 30 ml of distilled water are poured into a 1,000 ml flask and filled with distilled water to prepare a sample. 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured by a light scattering particle size analyzer (nano-zs, Malvern). When the average particle size of the large-diameter rubbery polymer is less than 400 nm, there is a possibility that the adhesive strength with the metal of the thermoplastic resin composition, the appearance characteristics (low lightness, etc.) may be lowered, and when it exceeds 1,500 nm, There exists a possibility that flame retardance, external appearance characteristics, etc. may fall.

In an embodiment, the large-diameter rubbery polymer (C) and the aromatic vinyl-based copolymer resin (D) are copolymerized with a rubbery polymer, an aromatic vinyl-based monomer, and the aromatic vinyl-based monomer having a viscosity of 150 cps or more in a 5% by weight styrene solution. Form of rubber-modified aromatic vinyl copolymer resin (large particle size rubbery polymer (C) having a mean particle size of 400 to 1,500 nm and continuous aromatic vinyl copolymer resin (D)) prepared by continuous solution polymerization of possible monomers It may be included in the thermoplastic resin composition.

Specifically, the rubber-modified aromatic vinyl copolymer resin is a mixture of the rubber polymer, the aromatic vinyl monomer, the monomer copolymerizable with the aromatic vinyl monomer and a solvent mixed with a polymerization initiator and a molecular weight modifier in a mixed solution to prepare a reaction solution To manufacture; Adding the reaction solution to a first reactor to polymerize at a conversion rate of 30 to 40%; In addition, the polymerized product polymerized in the first reactor may be prepared by polymerizing at a conversion rate of 70 to 80% by adding the polymerized product to the second reactor.

In an embodiment, the mixed solution may include 3 to 15 wt% of the rubbery polymer, 50 to 85 wt% of the monomer copolymerizable with the aromatic vinyl monomer and the aromatic vinyl monomer, and 5 to 30 wt% of the solvent.

In an embodiment, the rubbery polymer contained in the mixed solution may be hydrogenated to a diene rubber (rubber polymer) such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), or the diene rubber. An acrylate rubber (rubber polymer), such as a saturated rubber, an isoprene rubber, a polybutyl acrylate, an ethylene-propylene-diene monomer terpolymer (EPDM), etc. can be illustrated, but it is not limited to this. These can be applied individually or in mixture of 2 or more types. For example, diene rubber may be used, and specifically, polybutadiene rubber may be used. In addition, the rubbery polymer may have a viscosity in the 5 wt% styrene solution of 150 cps or more, for example, 150 to 300 cps, specifically 160 to 200 cps. In the styrene solution viscosity range, a large particle rubbery polymer may be prepared.

In an embodiment, the aromatic vinyl monomers included in the mixed solution include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene , Dibromostyrene, vinyl naphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types.

In a specific embodiment, as the monomer copolymerizable with the aromatic vinyl monomer contained in the mixed solution, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile And vinyl cyanide monomers such as fumaronitrile, and the like, and may be used alone or in combination of two or more thereof.

In embodiments, the content of the aromatic vinyl monomer may be 20 to 90% by weight, for example 30 to 80% by weight of the aromatic vinyl monomer and 100% by weight of the total copolymerizable monomer with the aromatic vinyl monomer, The content of the monomer copolymerizable with the aromatic vinyl monomer may be 10 to 80% by weight, for example 20 to 70% by weight, based on 100% by weight of the aromatic vinyl monomer and 100% by weight of the monomer copolymerizable with the aromatic vinyl monomer.

In an embodiment, an aromatic organic solvent may be used as the solvent. For example, ethylbenzene, xylene, toluene and the like can be used, and these can be used alone or in combination of two or more.

In embodiments, the polymerization initiator preferably has a half-life of 10 minutes or less at the reactor polymerization temperature, for example, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1- Bis (t-butylperoxy) cyclohexane, 2-bis (4,4-di-t-butylperoxycyclohexane) propane, t-hexyl peroxyisopropyl monocarbonate, t-butylperoxymaleic acid, t -Butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-butyl peroxy Isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, Radical initiators such as 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, n-butyl-4,4-bis (t-butyl peroxy) valerate and mixtures thereof Can be. The amount of the polymerization initiator used may be 0.007 to 0.07 parts by weight, for example, 0.01 to 0.05 parts by weight based on 100 parts by weight of the mixed solution. In the said range, the external appearance characteristic fall etc. by a residual polymerization initiator can be reduced.

In embodiments, the molecular weight modifier may be an alkyl mercaptan such as t-dodecyl mercaptan, n-dodecyl mercaptan and the like. The amount of the molecular weight modifier may be 0.02 to 1 part by weight, for example 0.03 to 0.5 part by weight, based on 100 parts by weight of the mixed solution.

In a specific embodiment, since the continuous solution polymerization may generate an exothermic phenomenon due to a polymerization reaction in the reactor, it is preferable to use a method of circulating a refrigerant through a jacket, a coil, or the like.

In an embodiment, the reaction solution to which the polymerization initiator and the molecular weight modifier are added may be added to the first reactor to polymerize a conversion rate of 30 to 40%, for example, 32 to 38%. In the above range, the polymerization can be stably performed without excessive load on the stirrer.

In embodiments, the reaction temperature in the first reactor may be 60 to 150 ° C, for example 70 to 130 ° C. The reaction temperature may be changed depending on the reactor, stirring speed, type of polymerization initiator, and the like.

In embodiments, the stirring speed in the first reactor may be 140 to 160 rpm. The stirring speed may be changed depending on the reactor size, the type of polymerization initiator, the reaction temperature, etc., and a large particle rubbery polymer may be prepared in the above range.

In an embodiment, the polymerized polymer in the first reactor is introduced into the second reactor, and the polymerization may be performed until the conversion rate is 70 to 80%. It is possible to produce a large particle rubbery polymer in the above range.

In embodiments, the reaction temperature in the second reactor may be 80 to 170 ℃, for example 120 to 160 ℃. The reaction temperature may be changed depending on the reactor, stirring speed, type of polymerization initiator, and the like.

In an embodiment, the stirring speed in the second reactor can be 75 to 85 rpm. The stirring speed may be changed depending on the reactor size, the type of polymerization initiator, the reaction temperature, etc., and a large particle rubbery polymer may be prepared in the above range.

In embodiments, the continuous solution polymerization may further comprise devolatilizing the polymerized polymer in the second reactor to remove unreacted monomer and residual solvent. The devolatilization process may be performed using a devolatilization tank. In one embodiment, the devolatilization process can be performed using a single devolatilization tank, and in other embodiments, the devolatilization process can remove residual unreacted material in the first and second devolatilization tanks connected vertically. When the devolatilization process is performed, the residual monomer content may be 1,500 ppm or less, for example, 1,000 ppm or less, specifically 700 ppm or less.

In an embodiment, the fall devolatilization device is a fall-stranding devolatilization (DEVO) type. The pole-stranding devolatilizer should be designed so that the angle of the cone minimizes residence time and can be effectively transmitted to the lower gear pump.

In an embodiment, when the first devolatilization tank and the second devolatilization tank are used in connection, vertical connection may be performed vertically upward and downward in order to minimize the connection line between DEVO. In addition, it is preferable that a control valve or a regulator is installed in the first devolatilization tank DV-1 to enable pressure adjustment.

In an embodiment, the first devolatilizer may be operated at a pressure of 100 to 600 torr, for example 200 to 500 torr, temperature of 160 to 240 ° C, for example 180 to 220 ° C, under a residence time of 10 minutes or less. Impurities, such as a residual monomer, can be reduced in the said range, and productivity may be excellent. In addition, the second devolatilization tank may be operated at a pressure of 1 to 50 torr and a temperature of 210 to 250 ° C. for 10 minutes or less, for example, 5 minutes or less. The color of the rubber-modified aromatic vinyl copolymer resin prepared in the above range may be excellent.

In an embodiment, the aromatic vinyl copolymer resin (D) of the rubber-modified aromatic vinyl copolymer resin (D) is a monomer mixture comprising a monomer copolymerizable with the aromatic vinyl monomer such as an aromatic vinyl monomer and a vinyl cyanide monomer. It may be a polymer, and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) may be 10,000 to 300,000 g / mol, for example, 15,000 to 150,000 g / mol. In the above range, the mechanical strength, moldability, and the like of the thermoplastic resin composition may be excellent.

In an embodiment, the large particle rubbery polymer (C) may be included in an amount of 0.5 to 5 parts by weight, for example, 1 to 3 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may have excellent adhesive strength, rigidity, appearance characteristics, impact resistance, fluidity (molding processability), and the like.

In an embodiment, the aromatic vinyl copolymer resin (D) may be included in an amount of 3 to 20 parts by weight, for example, 7 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the appearance characteristics of the thermoplastic resin composition, fluidity (molding processability) and the like may be excellent.

(E) Phosphorus Flame Retardant

The phosphorus flame retardant according to one embodiment of the present invention may be a phosphorus flame retardant used in a conventional flame retardant thermoplastic resin composition. For example, phosphorus-based flame retardants such as phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, and metal salts thereof Can be used. These may be used alone or in combination of two or more thereof.

In embodiments, the phosphorus flame retardant may include an aromatic phosphate ester compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ , R ₂ , R _4, and R ₅ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or a C 6 -C 20 aryl substituted with an alkyl group having 1 to 10 carbon atoms. R ₃ is a C 6 -C 20 arylene group substituted with a C 6 -C 20 arylene group or a C 1 -C 10 alkyl group, for example, dialcohol such as resorcinol, hydroquinone, bisphenol-A, bisphenol-S, etc. Derived from n is an integer from 0 to 10, for example from 0 to 4.

As the aromatic phosphate ester compound represented by the formula (1), when n is 0, diaryl phosphates such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trigylenyl phosphate, and tri (2,6-dimethyl) Phenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dimethylphenyl) phosphate, etc., and n is 1 Bisphenol-A bis (diphenylphosphate), resorcinol bis (diphenylphosphate), resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinol bis [bis (2,4) -Dibutylbutylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinone bis [bis (2,4-diarybutylphenyl) phosphate] and the like, but may be exemplified. It is not limited. These may be applied alone or in the form of mixtures of two or more.

In embodiments, the phosphorus-based flame retardant may be included in 10 to 30 parts by weight, for example 15 to 25 parts by weight based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may be excellent in flame retardancy, thermal stability, fluidity, and the like.

(F) talc

The talc according to one embodiment of the present invention, together with wollastonite, can improve the fluidity, rigidity, (thin film) flame retardancy, appearance characteristics, balance of physical properties, and the like of the thermoplastic resin composition.

In an embodiment, the talc can be a conventional plate-shaped talc. The average particle size of the talc may be 2 to 10 μm, for example 3 to 7 μm. In the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, appearance characteristics, and the like.

In embodiments, the talc may have a bulk density of 0.3 to 1.0 g / cm ³ , for example, 0.4 to 0.8 g / cm ³ . In the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, appearance characteristics, and the like.

In an embodiment, the talc may be included in an amount of 3 to 25 parts by weight, for example, 8 to 20 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may have excellent fluidity, dimensional stability, rigidity, and flame retardancy.

(G) wollastonite

The wollastonite according to one embodiment of the present invention, together with talc, can improve the fluidity, rigidity, (thin film) flame retardancy, appearance properties, balance of physical properties, and the like of the thermoplastic resin composition.

In one embodiment, wollastonite is a calcium-based mineral and is a white acicular mineral, and at least a part of the surface may be hydrophobic surface treated. Here, the hydrophobic surface treatment may be, for example, coated wollastonite with an olefin-based, epoxy-based, silane-based material, but is not limited thereto.

In embodiments, the wollastonite may have an average longitudinal length (diameter) of 5 to 10 μm, for example 6 to 9 μm, and an aspect ratio (length: width) of 1: 7 to 1: 9. In the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, impact resistance, and the like.

In embodiments, the wollastonite may have a bulk density of 0.3 to 0.6 g / cm ³ , for example 0.4 to 0.5 g / cm ³ . In the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, and the like.

In an embodiment, the wollastonite may be included in an amount of 5 to 20 parts by weight, for example, 7 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may have excellent fluidity, dimensional stability, rigidity, and flame retardancy.

In embodiments, the weight ratio of talc (F) and wollastonite (G) (F): (G) may be 1: 0.1 to 1: 5, for example, 1: 0.3 to 1: 2. In the above range, the thermoplastic resin composition may have excellent dimensional stability, rigidity, and the like.

(H) Rubbery polymer in which maleic anhydride is graft-polymerized

The rubbery polymer polymerized with maleic anhydride according to one embodiment of the present invention improves the compatibility, dispersibility, etc. of components of the thermoplastic resin composition, thereby improving flowability, impact resistance, thermal stability, dimensional stability, In order to improve appearance characteristics, maleic anhydride (MAH, maleic anhydride, etc.) may be graft-polymerized to a rubbery polymer (copolymer of an olefin and / or an aromatic vinyl monomer).

In an embodiment, the rubbery polymer in which maleic anhydride is graft-polymerized is ethylene-octene rubber (MAH-g-EOR) in which maleic anhydride is graft-polymerized, and ethylene-butene rubber in which maleic anhydride is graft-polymerized (MAH -g-EBR), ethylene-propylene-diene monomer terpolymer (MAH-g-EPDM) graft polymerized maleic anhydride, styrene-ethylene-butadiene-styrene copolymer graft polymerized maleic anhydride (MAH -g-SEBS), maleic anhydride may comprise one or more of graft polymerized polypropylene (MAH-g-PP) and maleic anhydride graft polymerized polyethylene (MAH-g-PE).

In an embodiment, the rubbery polymer to which the maleic anhydride is graft polymerized may be selected from olefins such as ethylene and alpha-olefins; And it may be prepared by graft polymerization of maleic anhydride to a rubbery polymer which is a copolymer of a monomer mixture comprising an aromatic vinyl monomer such as styrene. For example, the rubbery polymer in which the maleic anhydride is graft-polymerized is a styrene-ethylene-butadiene-styrene (SEBS) having a melt flow index (MI) of 10 to 50 g / 10 minutes using a twin screw extruder. Peroxides may be added to rubbery polymers such as copolymers to break ethylene bonds, and free radicals may be produced by a reaction extrusion method in which maleic anhydride is introduced into ethylene bonds.

In an embodiment, the maleic anhydride may be 0.1-3 wt% of the maleic anhydride in 100 wt% of the graft copolymerized rubber # 100 wt%, and the content of the rubbery polymer may be 95-99.9 wt%, This is not restrictive.

In one embodiment, the maleic anhydride graft polymerized rubbery polymer may be included in an amount of 0.01 to 5 parts by weight, for example 0.1 to 3 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may have excellent fluidity, thermal stability, appearance characteristics, and the like.

(I) black pigment

The black pigment according to an embodiment of the present invention can improve the appearance characteristics, rigidity, and the like of the thermoplastic resin composition. For example, carbon black or the like may be used as the black pigment.

In embodiments, the black pigment may have an average particle size (D50, volume average) measured by a particle size analyzer of 10 to 24 nm, for example 15 to 22 nm. In the above range, the appearance characteristics such as color of the thermoplastic resin composition may be excellent.

In an embodiment, the black pigment may be included in an amount of 0.05 to 3 parts by weight, for example, 0.3 to 2 parts by weight, based on 100 parts by weight of the polycarbonate resin. In the above range, the thermoplastic resin composition may have excellent appearance characteristics, rigidity, and flame retardancy.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive such as a release agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant aid, an antidropping agent, an antioxidant, a mixture thereof, and the like.

In an embodiment, as the additive, an additive used in a conventional thermoplastic resin composition may be used without limitation. For example, the additives include mold release agents such as polyethylene wax, fluorine-containing polymer, silicone oil, metal salt of stearyl acid, metal salt of montanic acid and montanic acid ester wax; Nucleating agents such as clay; Antioxidants such as hindered phenol compounds; Mixtures thereof and the like may be used, but are not limited thereto. The additive may be included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polycarbonate resin, but is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets which are mixed with the above components and melt-extruded at 200 to 280 ° C, for example, 250 to 260 ° C, using a conventional twin screw extruder.

In an embodiment, the thermoplastic resin composition is bonded according to ASTM D1002, 100 mm × 25 mm × 2 mm size injection specimen with an adhesive to overlap the same size metal specimen and 25 mm × 25 mm area, and then at 80 ℃ After the adhesion site is heated for 120 seconds and then aged at room temperature for 5 minutes, the measured adhesive strength (shear strength) may be 140 to 300 kgf / cm ² , for example 150 to 250 kgf / cm ² .

In an embodiment, the thermoplastic resin composition may have a flame retardancy of 1.0 mm thick specimen measured by the UL-94 vertical test method of V-1 or more.

In embodiments, the thermoplastic resin composition has a melt-flow index (MI) of 40 to 60 g / 10 minutes, for example 45 to 55, measured at 220 ° C. and 5 kgf in accordance with ASTM D1238. g / 10 minutes.

The molded article according to the present invention is formed from the thermoplastic resin composition.

In an embodiment, the molded article may be a plastic member of an electronics housing including a metal frame and a plastic member in contact with at least one surface of the metal frame.

1 is a schematic cross-sectional view of an electronics housing according to an embodiment of the present invention. In the drawings, the sizes of components constituting the invention are exaggerated for clarity and are not limited thereto. As shown in FIG. 1, an electronics housing according to an embodiment of the present invention includes a metal frame 10; And at least one plastic member 20 in contact with at least one surface of the metal frame 10, wherein the plastic member is formed from the thermoplastic resin composition.

In an embodiment, the shape of the metal frame 10 and the plastic member 20 is not limited to the drawings and may have various shapes. However, the metal frame 10 and the plastic member 20 have a structure in which at least one surface is in contact with each other. The contact structure may be implemented by adhesion or insertion, and the method of contacting is not limited.

In an embodiment, the metal frame 10 may be a product applied to a conventional electronic housing, such as a stainless steel frame, the plastic member, and is easy to purchase commercially.

In an embodiment, the plastic member 20 may be formed from the polycarbonate resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Specifically, the plastic member 20 may be molded by a hot water mold method or a steam mold method (rapid heat cycle molding (RHCM) method, etc.), and may be a front cover of a 22 to 85 inch thin film television, a thin film monitor, or the like. cover, rear cover, and the like. The plastic member 20 can be applied to appearance specifications such as a hairline pattern and a corrosion pattern.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, the specification of each component used in the Example and the comparative example is as follows.

(A) polycarbonate resin

Bisphenol-A type polycarbonate resin (flow index (MI, measured at 300 degreeC and 1.2 kg conditions based on ISO 1133): 90 +/- 10 g / 10min) was used.

(B) Rubber-modified vinyl graft copolymer

45-wt% butadiene rubber (average particle size: 310 nm) was used g-ABS graft copolymerized with 55 wt% styrene and acrylonitrile (weight ratio 75/25).

(C) Large particle rubbery polymer and (D) aromatic vinyl copolymer resin

(C1) Large-diameter rubbery polymer and (D1) aromatic vinyl copolymer resin: 5% by weight of a styrene solution in a mixed solution consisting of 53.4 parts by weight of styrene monomer, 17.8 parts by weight of acrylonitrile monomer, and 20 parts by weight of ethylbenzene as a reaction solvent. 8.8 parts by weight of butadiene rubber (BR-1: ASADENE 55AE) having a solution viscosity of 170 cps was dissolved, and 0.015 parts by weight of 1,1-bis (t-butylperoxy) cyclohexane as a polymerization initiator and t as a molecular weight regulator were used. -0.07 parts by weight of dodecyl mercaptan was added to prepare a mixed solution. The prepared mixed solution was introduced into the reactor at a rate of 25 kg / hr. The first reactor regulated the stirring speed to 150 rpm and the conversion rate to 35% level. In the second reactor, the stirring speed was controlled at 80 rpm, the conversion rate was polymerized to 75% level, and then the remaining unreacted material was removed through a devolatilization tank. A mixture of a large particle rubbery polymer ((C1), dispersed phase) and an aromatic vinyl copolymer resin (SAN resin (D1), continuous phase) (content (dispersion phase: continuous phase: 12% by weight: 88% by weight)) was prepared. It was. Here, the average particle size of the large-diameter rubbery polymer (C1) was 591 nm, and the weight average molecular weight of the SAN resin (D1) was 130,000 g / mol.

(C2) rubbery polymer and (D2) aromatic vinyl copolymer resin: (C1) and (A) except that the stirring speed of the first reactor was changed to 170 rpm and the second reactor stirring speed was changed to 90 rpm. In the same manner as in (D1), a mixture of rubber-modified aromatic vinyl copolymer resin (ABS resin, rubbery polymer (C2, dispersed phase) and aromatic vinyl copolymer resin (SAN resin, D2, continuous phase) (content ( Dispersed phase: continuous phase): 12% by weight: 88% by weight)). Here, the average particle size of the prepared rubbery polymer (C2) was 305 nm, the weight average molecular weight of the SAN resin (D2) was 130,000 g / mol.

(C3) rubbery polymer and (D3) aromatic vinyl copolymer resin: (C1) and (A) except that the stirring speed of the first reactor was changed to 130 rpm and the stirring speed of the second reactor was changed to 70 rpm. In the same manner as in (D1), a mixture of rubber-modified aromatic vinyl copolymer resin (ABS resin, rubbery polymer (C3, dispersed phase) and aromatic vinyl copolymer resin (SAN resin, D3, continuous phase) (content ( Dispersed phase: continuous phase): 12% by weight: 88% by weight)). Here, the average particle size of the prepared rubber polymer (C3) was 5,160 nm, the weight average molecular weight of the SAN resin (D3) was 130,000 g / mol.

(E) Phosphorus Flame Retardant

Oligomeric bisphenol-A diphosphate (bisphenol-A diphosphate, manufactured by Yoke Chemical, product name: YOKE BDP) was used.

(F) talc

Talc (manufacturer: KOCH, product name: KCM 6300, bulk density: 0.4 to 0.6 g / cm ³ ) was used.

(G) wollastonite

Wollastonite (manufacturer: NYCO, product name: 4W, bulk density: 0.4 to 0.5 g / cm ³ ) was used.

(H) Rubbery polymer in which maleic anhydride is graft-polymerized

MAH-g-EBR (manufacturer: Mitsui, product name: TAFMER) was used.

(I) black pigment

Carbon black (manufacturer: OCI, product name: HIBLACK, average particle size: 18 nm) was used.

Example  1 to 4 and Comparative example  1 to 5

Each of the components was added in an amount as described in Table 1 below, followed by extrusion at 250 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder having a diameter of L / D = 36 and 45 mm, and the pellets were dried at 80 ° C. for at least 4 hours, and then injected in a 6 Oz injection machine (molding temperature 250 to 260 ° C., mold temperature: 60 ° C.). To prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Table 1 below.

Property measurement method

(1) Adhesive strength (shera stress, unit: kgf / cm ² ): According to ASTM D1002, 100 mm × 25 mm × 2 mm injection molded specimens are the same size as metal (aluminum) specimens and 25 mm × Bond with an adhesive (manufacturer: Henkel, product name: LOCTITE HF8150R) to overlap the 25 mm area, use a heat gun to heat the adhesive site for 120 seconds at 80 ° C, and then age at room temperature for 5 minutes. After aging), the adhesive strength was measured.

(2) Flame retardancy: According to the UL-94 vertical test method, it was measured using a 1.0 mm thick specimen.

(3) Melt-flow index (MI, unit: g / 10 min): Measured under the conditions of 220 ° C. and 5 kgf according to ASTM D1238.

Example Comparative example One 2 3 4 One 2 3 4 5 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 5 5 5 5 15 5 5 5 5 (C1) (parts by weight) 1.2 1.8 2.4 1.8 - 1.8 1.8 - - (C2) (parts by weight) - - - - - - - 1.8 - (C3) (parts by weight) - - - - - - - - 1.8 (D1) (parts by weight) 8.8 13.2 17.6 13.2 - 13.2 13.2 - - (D2) (parts by weight) - - - - - - - 13.2 - (D3) (parts by weight) - - - - - - - - 13.2 (E) (parts by weight) 20 20 20 20 20 20 20 20 20 (F) (parts by weight) 10 10 10 15 10 - 15 10 10 (G) (parts by weight) 5 5 5 5 5 15 - 5 5 (H) (parts by weight) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 (I) (parts by weight) One One One One One One One One One Adhesive strength 150 190 210 160 90 130 110 120 200 Flame retardancy V-0 V-0 V-1 V-1 V-0 V-1 V-1 V-1 V-2 Melt flow index 45 50 55 45 35 45 35 40 35

From the results of Table 1, it can be seen that the thermoplastic resin composition of the present invention is excellent in adhesive strength (adhesive strength), flame retardancy (flame retardancy), fluidity (melt flow index), etc. with the metal, stiffness, dimensional stability, appearance characteristics It was confirmed that the back is excellent.

On the other hand, in the case of Comparative Example 1, which does not use a large-diameter rubbery polymer and an aromatic vinyl copolymer resin, it can be seen that the adhesive strength, etc. are lowered, the fluidity is lowered relative, in the case of Comparative Example 2 that does not use talc It turns out that adhesive strength etc. fall, and it turns out that adhesive strength etc. fall in the comparative example 3 which does not use wollastonite. In Comparative Example 4 in which the rubbery polymer (C2) and the aromatic vinyl-based copolymer resin (D2) were used instead of the large-diameter rubbery polymer (C1) and the aromatic vinyl-based copolymer resin (D1) of the present invention, the adhesive strength and the like decreased. In the case of Comparative Example 5 in which the rubbery polymer (C3) and the aromatic vinyl-based copolymer resin (D3) were used instead of the large-diameter rubbery polymer (C1) and the aromatic vinyl copolymer resin (D1) of the present invention, It can be seen that the flame retardancy and the like is reduced.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (14)

Polycarbonate resins;
Rubber modified vinyl graft copolymers;
Large particle rubbery polymers having an average particle size of 400 to 1500 nm;
Aromatic vinyl copolymer resins;
Phosphorus flame retardants;
Talc;
Wollastonite;
Rubbery polymers in which maleic anhydride is graft polymerized; And
A thermoplastic resin composition comprising a black pigment.
According to claim 1, wherein the thermoplastic resin composition is 100 parts by weight of the polycarbonate resin; 1 to 10 parts by weight of the rubber-modified vinyl graft copolymer; 0.5 to 5 parts by weight of the large particle rubbery polymer; 3 to 20 parts by weight of the aromatic vinyl copolymer resin; 10 to 30 parts by weight of the phosphorus flame retardant; 3 to 25 parts by weight of the talc; 5 to 20 parts by weight of the wollastonite; 0.01 to 5 parts by weight of the rubbery polymer graft polymerized maleic anhydride; And 0.05 to 3 parts by weight of the black pigment.
According to claim 1, The rubber-modified vinyl graft copolymer is characterized in that the graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer having an average particle size of 100 to 600 nm Thermoplastic resin composition.
According to claim 1, wherein the large-diameter rubbery polymer and the aromatic vinyl copolymer resin is a continuous polymer of a rubbery polymer having an viscosity of at least 150 cps in a 5% by weight styrene solution, an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer What is included in the thermoplastic resin composition in the form of a rubber-modified aromatic vinyl copolymer resin prepared by solution polymerization (a mixture of a large particle size rubbery polymer having a mean particle size of 400 to 1,500 nm in a dispersed phase and an aromatic vinyl copolymer resin in a continuous phase) The thermoplastic resin composition characterized by the above-mentioned.
The thermoplastic resin composition of claim 1, wherein the aromatic vinyl copolymer resin is a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
The thermoplastic resin composition of claim 1, wherein the phosphorus-based flame retardant comprises at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, and a phosphazene compound.
The thermoplastic resin composition according to claim 1, wherein the weight ratio of talc and wollastonite is 1: 0.3 to 1: 2.
The rubbery polymer of claim 1, wherein the maleic anhydride is graft-polymerized is an ethylene-octene rubber (MAH-g-EOR) in which maleic anhydride is graft-polymerized, and an ethylene-butene rubber in which maleic anhydride is graft-polymerized. (MAH-g-EBR), ethylene-propylene-diene monomer terpolymer (MAH-g-EPDM) graft polymerized maleic anhydride, styrene-ethylene-butadiene-styrene copolymer graft polymerized maleic anhydride (MAH-g-SEBS), that maleic anhydride comprises at least one of graft polymerized polypropylene (MAH-g-PP) and maleic anhydride in graft polymerized polyethylene (MAH-g-PE) The thermoplastic resin composition characterized by the above-mentioned.
The thermoplastic resin composition of claim 1, wherein the average particle size of the black pigment is 10 to 24 nm.
According to claim 1, The thermoplastic resin composition according to ASTM D1002, 100 mm × 25 mm × 2 mm injection molded specimens with an adhesive to overlap the same size metal specimen and 25 mm × 25 mm area, and then 80 The adhesive site was heated at 120 ° C. for 120 seconds, and then aged at room temperature for 5 minutes, and the measured adhesive strength (shear strength) was 140 to 300 kgf / cm ² .
The method of claim 1, wherein the thermoplastic resin composition is a thermoplastic resin composition, characterized in that the flame retardancy of the 1.0 mm thick specimen measured by the UL-94 vertical test method is V-1 or more.
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a melt-flow index (MI) of 30 to 60 g / 10 minutes measured at 220 ° C. and 5 kgf according to ASTM D1238. Resin composition.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 12.
The molded article of claim 13, wherein the molded article is a plastic member of an electronics housing including a metal frame and a plastic member contacting at least one surface of the metal frame.

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